Functional norbornenes and polymeric derivatives and fabrication thereof

ABSTRACT

The invention relates to functional norbornenes as initiators for radical polymerization, its polymer and fabrication method thereof. More particularly, the functional norbornenes can be selectively polymerized by ring-opening metathesis polymerization or radical polymerization to obtain various polynorbornene derivatives or grafted copolymer materials. The polynorbornene derivatives and grafted copolymer materials not only exhibit excellent functional properties but also enhanced physical and chemical properties after modification. The polynorbornene derivatives and grafted copolymer materials disclosed in the invention exhibit excellent heat resistance, transparency and water resistance. The invention also deals with a process for producing such derivatives and materials having controllable molecular weight with narrow molecular weight distribution.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 10/777,054,filed Feb. 13, 2004, which is now allowed and all disclosures of theapplication are incorporated herewith by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a series of high performance polymericmaterials derived from norbornene derivatives and particularly tofunctional norbornenes as initiators for radical polymerization andpolymers thereof.

2. Description of the Related Art

Polycarbonate (PC) has commonly been used as macromolecular material foroptical purposes. Considerations which may influence the use of theoptical material include birefringence and water adsorption. With thedevelopment of high-density compact disks, it has become more difficultfor the conventional polymers to meet such requirements.

A commercial material ZEONEX has been developed by Nippon Zeon, apolynorbornene with lower birefringence and water adsorption andimproved optical characteristics. Such material can be prepared byring-opening metathesis polymerization of a norbornene monomer in thepresence of a metathesis catalyst and hydrogenated to become a saturatedpolynorbornene.

With the development of high-density compact disks, a method forproducing a new polymeric material with lower birefringence and hightransmittance for low wavelength range (blue light) has been developed.Non-crtystallinity of the polynorbornene is such that transmittance withrespect to light of wavelength about 400 nm may approach 90%, since noaromatic ring is present in the main chain. In addition, the absence ofa hydrophilic functional group in the main chain allows a ratio of wateradsorption below 0.01%. Under the same condition, the polynorbornene haswater absorption ratio far lower than that of the polycarbonate (PC).Further, glass transition temperatures of the polynorbornene andpolycarbonate (PC) fall within the same temperature range (about 123°C.).

Recent attention has been paid to hydrogenated products of polymersproduced by ring-opening metathesis polymerization of norbornene-typemonomers such as tetracyclododecene, dicyclopentadiene (DCP), andtricyclopentadiene, etc. These hydrogenated products can serve asoptical material for use in an optical disk, optical lens, ortransparent film, etc. (see JPO60-26024, JPO1-24826, JPO63-264626,EP303, 246, JPO-63-317520 and JPO-1-132656), since such hydrogenatedproducts have excellent transparency and heat resistance and lowsusceptibility to moisture gain, with comparatively low briefringenceand excellent moldability.

Olefin metathesis polymerization is a popular method in polymersynthesis. In recent years, the ring-opening metathesis polymerizationof cycloolefin and the metathesis polymerization of non-cyclodiolefinhave become very important in polymer synthesis. Along with developmentof new catalysts, the synthesis method of polymeric materials whichcontain various functional groups has further developed correspondingly.

While organometallic catalyst use in metathesis polymerization has beenpopular for some time, the organometallic catalysts are not suitable inmetathesis polymerization of the monomer which contains variousfunctional groups and is also sensitive to moisture and oxygen gas. Forexample, tungsten (W), titanium (Ti), molybdenum (Mo) and ruthenium (Ru)catalysts are the most popular catalysts used in the ring-openingmetathesis polymerization of cycloolefin, wherein ruthenium (Ru)catalyst is the most tolerant catalyst with respect to water and oxygengas in the metathesis polymerization. The metathesis polymerization canbe carried out in an aqueous solution in the presence of ruthenium (Ru)catalyst. For example, the catalyst of {Cl₂Ru(CHPh)[P(C₆H₁₁)₃]₂}developed by Grubbs et al. in 1996 is suitable for ring-openingmetathesis polymerization of cycloolefin. More particularly, thepolymerization of the monomers with functional groups can be carried outin the presence of such a catalyst because it is stable in air. Inaddition, such metathesis polymerization provides a high polymerizationrate and large molecular weight of resulting polymer. Generallyspeaking, such reaction has accompanied with living polymerization.

The ring-opening metathesis polymerization of a norbornene-type monomeris carried out, in general, in the presence of a catalyst systemconsisting of an organometallic compound such as an organoaluminumcompound and a tungsten and/or molybdenum-based metathesis catalyst(please refer to JPO46-14910), or a catalyst system containing anorganometallic compound such as an organoaluminium compound and atransition-metal compound such as titanium tetrahalide (please refer toJPO41-20111 and JPO50-12199).

However, with use of the first catalyst system, the resultant polymerhas a broad distribution of molecular weight and thus highbirefringence, despite being obtainable in such high yields, that theresidual monomer is minimally present in the reaction system when thereaction is complete.

With use of the second system, the molecular weight distribution ofresulting polymer can be easily controlled. However, as theconcentration of monomer in the reaction system decreases, the rate ofpolymerization also decreases accordingly. Hence, polymers by thering-opening metathesis polymerization (ROMP) of the present catalystsystem cannot be obtained in high yields. Moreover, a large amount ofunreacted monomer remains in the reaction system when the polymerizationhas completed. It is very difficult to remove this unreacted monomerduring purification of the polymer.

Hence, extensive research has been directed at ring-opening metathesispolymerization (ROMP) of cycloolefin derivatives to improve thereactivity of catalysts, focused on the development of side-chain-typeliquid crystal, a triblock copolymer synthesized by two-step method, apolymer with various functional groups and a polymer havingcross-linkable functional groups remained in the side chain thereof,etc. The introduction of the functional groups improves the opticalcharacteristics and biochemical activity of the polymer. In addition,the cross-linkable functional groups such as methacryloyl in theside-chain can be introduced and applied as UV curing agent, coatingmaterial and photoresist.

Polynorbornene and its derivatives, the first commercial productsgenereated by ring-opening metathesis polymerization (ROMP), are animportant engineering material. The materials are used with shape-memorypolymers, shining apparatus, machine, electrical elements, tube, foodpackages and the like because of good transmittance, wide usabletemperature range, good mechanical properties, and excellentmoldability. In addition, the derivatives of polynorbornene such asacidic and aromatic polymers can serve as a photoresist for use insemiconductor manufacturing.

Although the polynorbornene and its derivatives have good transmittance,wider usable temperature range, good mechanical properties and excellentmoldability, synthesis of new norbornene-type monomers and polymers arenot well developed and problems associated therewith not easilyovercome. Hence, the development of new norbornene-type monomers andtheir derivatives has great potential in various applications.

BRIEF SUMMARY OF THE INVENTION

The invention provides functional norbornenes as initiators for radicalpolymerization, polymers, and fabrication method thereof. Moreparticularly, the polymerization of functional norbornenes in theinvention can be selectively carried out by ring-opening metathesispolymerization (ROMP) or radical graft copolymerization to obtainvarious polynorbornene derivatives (Macromonomer, macroinitiator,homopolymer, random copolymer and block copolymer) or grafted copolymermaterials(Branched polymeric materials). The polynorbornene derivativesand grafted copolymer materials exhibit not only excellent functionalproperties but also enhanced physical and chemical properties aftermodification.

A initiator was synthesized by the reaction of norbornene methyleneamine with 2-bromo-2-methylpropionyl bromide (Scheme I). A macromonomer,polymethylmethacrylate containing norbornyl end group (NBPMMA), wasprepared by radical polymerization using NBMBrMP as an initiator (SchemeII). Poly(macromonomer), poly(NBPMMA) with high molecular weight(Mn=6.8×10⁴) was obtained by polymerizing relatively low molecularweight (Mn=6.4×10³) NBPMMA. Since homopolymerization of NBPMMAmacromonomer with average molecular weight (Mn)1.3×10⁴ did not undergoring-opening metathesis polymerization (ROMP) with Ru complex{Cl₂Ru(CHPh)[P(C₆H₁₁)₃]₂}, ring-opening metathesis copolymerization ofmacromonomer containing norbornene end group (NBPMMA) and norbornenederivative containing carbazole group (NBCbz) was investigated. Therandom copolymer, poly(NBPMMA-co-NBCbz) with number-average molecularweight (Mn) 4.8×10⁴ and molecular weight distribution (PDI) 1.78 (SchemeIII) was successfully obtained. Fluorescent spectrum ofpoly(NBPMMA-co-NBCbz) exhibited strong emissions at 370 nm, 385 nm, 410nm and 440 nm due to carbazole group. Poly(NBPMMA-co-NBCbz) did notexhibit Tg; however, NBPMMA macromonomer (Mn=1.3×10⁴) exhibited Tg at110° C. due to polymethylmethacrylate segment. In addition, a newmacroinitiator, poly(HNBMBrMP), for radical polymerization was alsosynthesized by ROMP and hydrogenated (Scheme IV). Graft copolymerizationof poly(HNBMBrMP) with MMA was carried out in diluted macroinitiatorsolution ([poly(HNBMBrMP)]=3.64×10⁻² mol.L-1 in toluene) to yieldpoly(HNBMBrMP-g-PMMA) [Mn=2.0×10⁴, PDI=1.9] (Scheme IV). The signals ofamide hydrogen (6.7 ppm), PMMA segment [—CH₂C(CH₃)COOCH₃: 1.8˜1.9 ppm,—CH2C(CH3)COOCH3: 0.9˜1.6 ppm and —CH2C(CH3)COOCH₃: 3.4 ppm] appeared inthe 1 HnmR spectrum. The GPC results and the 1 HnmR spectral dataconfirmed the formation of the poly(HNBMBrMP-g-PMMA).

A first aspect of the invention comprises synthesis of a diblockmacroinitiator containing polynorbornene and carbazole segments. Thediblock macroinitiator containing norborene and carbazole segments isrepresented by:

wherein X is Br or Cl. Preferably, the diblock macroinitiator ispresented from a mixture of cabazole-containing norbornene-type monomer(II) in the presence of a catalyst via ring-opening metathesispolymerization(ROMP). An additional norbornene derivative(III) was addedto the reaction mixture after 15˜120 mins of ring-opening metathesispolymerization(ROMP) and the diblock macroinitiator is obtained.

wherein X is Br or Cl. More preferably, the metathesis catalyst is{Cl₂Ru(CHPh)[P(C₆H₁₁)₃]₂}.

A second aspect of the invention, a polynorbornene-containing graftedcopolymer comprising the formula (IA) is presented. Thepolynorbornene-containing graft copolymer is prepared using a diblockmacroinitiator with the formula

wherein X is Br or Cl; and

R is

A third aspect of the invention is the development of a process forpreparation of a grafted polynorbornene with the formula (IA),comprising preparation of a macroinitiator with the formula (I) byreaction of cabazole-containing norbornene-type monomer (II) and acatalyst via ring-opening metathesis polymerization and an additionalnorbornene dervative(III) being added to the mixture after 15˜120 minsof commencing ring-opening metathesis polymerization, preparation of amixture of Cu(I)Br,2,2′-bipyridine, the macroinitiator (I) and a monomercomprising

and preparation of the grafted polynorbornene copolymer with the formula(IA) by a graft copolymerization of the mixture under thermallyactivated condition and temperatures from 50 to 150° C., wherein

wherein X is Br or Cl; and

R is

A fourth aspect of the invention comprises synthesis of athermally-stable saturated cyclic aliphatic diblock macroinitiatorcomprising the formula (IV). The thermally-stable saturated cyclicaliphatic diblock macroinitiator is prepared by hydrogenating a diblockmacroinitiator with the formula (I):

wherein X is Br or Cl.

A fifth aspect of the invention comprises synthesis of apolynorbornene-containing grafted copolymer comprising the formula(IVA). The polynorbornene-containing grafted copolymer (IVA) is preparedby graft copolymerization of a diblock macroinitiator with the formula(IV):

wherein X is Br or Cl; and

R is

A sixth aspect of the invention comprises a process for preparing agrafted polynorbornene with the formula (IVA), comprising preparation ofa macroinitiator with the formula (I) by reaction of cabazole-containingnorbornene-type monomer (II) and a catalyst via ring-opening metathesispolymerization and addition of additional norbornene dervative(III) tothe reaction mixture after 15˜120 mins of ring-opening metathesispolymerization, hydrogenation of the diblock macroinitiator with theformula (I) to prepare a thermaly-stable saturated cyclic aliphaticdiblock macroinitiator with the formula (IV),preparation of a mixture ofCu(I)Br,2,2′-bipyridine, the thermally-stable saturated cyclic aliphaticdiblock macroinitiator (IV) and a monomer of

and preparation of the grafted polynorbornene copolymer with the formula(IVA) by graft copolymerization of the mixture at various temperaturesfrom 50 to 150° C., wherein

wherein X is Br or Cl; and

R is

A seventh aspect of the invention comprises synthesis of anorbornene-containing macrmonomer comprising formula (V), prepared usinga norbornene end group-containing initiator with the formula (III):

wherein X is Br or Cl; and

R is

An eighth aspect of the invention comprises synthesis of a norborneneend group-containing macrmonomer with the formula (V), comprisingpreparation of a mixture of Cu(I)Br,2,2′-bipyridine, a norbornene-typeinitiator (III) and a monomer of

and preparation of the norbornene end group-containing macromonomer withthe formula (V) by radical polymerization of the mixture at varioustemperatures from 50 to 150° C., wherein

wherein X is Br or Cl; and

R is

A ninth aspect of the invention comprises preparation of norbornene-typemacroinitiator comprising the formula (VI), by ring-opening metathesispolymerization using a catalyst and a norbornene-type dervative with theformula (III):

wherein X is Br or Cl.

A tenth aspect of the invention comprises a polynorbornene-containinggrafted copolymer comprising the formula (VII), prepared by graftcopolymerization using a macroinitiator with the formula (VI):

wherein X is Br or Cl; and

R is

An eleventh aspect of the invention comprises synthesis of a saturatedcyclic aliphatic polynorbornene-containing grafted copolymer comprisingthe formula (IX), prepared by graft copolymerization using a saturatedcyclic aliphatic macroinitiator with the formula (VIII):

wherein X is Br or Cl; and

R is

A twelfth aspect of the invention, a process for preparing graftedpolynorbornene copolymer with the formula (VII) is revealed. The processfor preparation of grafted polynorbornene copolymer (VII) comprises offollowing steps:

a) polymerization of a norbornene monomer with the formula (III) byring-opening metathesis polymerization using a catalyst to obtain amacroinitiator with the formula (VI);

b) preparation of a mixture of Cu(I)Br,2,2′-bipyridine, themacroinitiator (VI) and a monomer of

c) preparation of the grafted polynorbornene copolymer with the formula(VII) by a graft copolymerization of the mixture at various temperaturesfrom 50 to 150° C., wherein

wherein X is Br or Cl; and

R is

A thirteenth aspect of the invention comprises a process for preparinggrafted polynorbornene copolymer with the formula (IX) comprisespolymerization of a norbornene monomer with the formula (III) byring-opening metathesis polymerization using a catalyst to obtain amacroinitiator with the formula (VI), preparation of a mixture ofCu(I)Br,2,2′-bipyridine, the macroinitiator (VI) and a monomer of

hydrogenation of the macroinitiator with the formula (VII) to prepare athermally-stable saturated cyclic aliphatic macroinitiator with theformula (VIII), and preparation of a grafted polynorbornene with theformula (IX) by radical polymerization of the mixture at varioustemperatures from 50 to 150° C., wherein

wherein X is Br or Cl; and

R is

A fourteenth aspect of the invention comprises synthesis of anorbornene-type compound containing bromo-end group with the formula(XI):

-   -   wherein X is Br or Cl;    -   R₁ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—,    -   wherein n denotes an integer from 1 to 4; and    -   R₂ is H or —CH₃.

A fourteenth aspect of the invention comprises a polynorbornene-typemacroinitiator containing halogen-side group, with the formula (XII):

wherein X is Br or Cl;

R₁ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—,

wherein n denotes an integer from 1 to 4; and

R₂ is H or —CH₃ . Preferably, the macroinitiator is prepared from ahalogen-containing norbornene-type compound (XI) in the presence ofcatalyst via ring-opening metathesis polymerization, wherein

More preferably, the metathesis catalyst is {Cl₂Ru(CHPh)[P(C₆H₁₁)₃]₂}.

A fifteenth aspect of the invention comprises a thermally-stablesaturated cyclic aliphatic macroinitiator comprising the formula (XIII),prepared by hydrogenating a macroinitiator with the formula (XII):

wherein X is Br or Cl;

R₁ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—, wherein n denotes aninteger from 1 to 4; and

R₂ is H or —CH3.

A sixteenth aspect of the invention comprises a grafted polynorbornenecopolymer comprising the formula (XIV), prepared by graftcopolymerization using a macroinitiator with the formula (XIII):

wherein X is Br or Cl;

R₁ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—, wherein n denotes aninteger from 1 to 4;

R₂ is H or —CH₃; or

R is

A seventeenth aspect of the invention comprises a process for preparinggrafted polynorbornene copolymer with the formula (XIV), comprisingpolymerization of a norbornene monomer with the formula (XI) byring-opening metathesis polymerization using a catalyst to obtain amacroinitiator with the formula (XII), hydrogenation of themacroinitiator with the formula (VII) to prepare a thermally-stablesaturated cyclic aliphatic macroinitiator with the formula (VIII),preparation of a mixture of Cu(I)Br,2,2′-bipyridine, thethermally-stable saturated cyclic aliphatic macroinitiator (VIII) and amonomer of

and preparation of a grafted polynorbornene with the formula (XIV) byradical polymerization of the mixture at various temperatures from 50 to150° C., wherein

wherein X is Br or Cl;

R₁ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—,

wherein n denotes an integer from 1 to 4;

R₂ is H or —CH₃; or

R is

An eighteenth aspect of the invention comprises a process for preparinggrafted polynorbornene copolymer with the formula (XIVA), comprisingpolymerization of a norbornene monomer with the formula (XI) byring-opening metathesis polymerization using a catalyst to obtain amacroinitiator with the formula (XII), hydrogenation of themacroinitiator with the formula (XII) to prepare a thermally-stablesaturated cyclic aliphatic macroinitiator with the formula (XIII),preparation of a mixture of Cu(I)Br,2,2′-bipyridine, thethermally-stable saturated cyclic aliphatic macroinitiator (VIII) and amonomer of

and preparation of a grafted polynorbornene with the formula (XIVA) byradical polymerization of the mixture at various temperatures from 50 to150° C., wherein

wherein X is Br or Cl;

R₁ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—,

wherein n denotes an integer from 1 to 4;

R₂ is H or —CH₃; or

R is

A nineteenth aspect of the invention comprises a process for preparingnorbornene end group-containing macromonomer with the formula (XV),comprising preparation of a mixture of Cu(I)Br,2,2′-bipyridine,anorbornene derivative (XI) and a monomer of

and preparation of a norbornene end group-containing macromonomer withthe formula (XV) by radical polymerization of the mixture at varioustemperatures from 50 to 150° C., wherein

wherein X is Br or Cl;

R¹ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—,

wherein n denotes an integer from 1 to 4;

R₂ is H or —CH₃; or

R is

A twentieth aspect of the invention comprises a norbornene endgroup-containing macromonomer comprising formula (XV):

wherein X is Br or Cl;

R₁ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—,

wherein n denotes an integer from 1 to 4;

R₂ is H or —CH₃; or

R is

A twenty first aspect of the invention comprises a copolymer containingcarbazole and halo-side groups, comprising formula (XVI):

wherein X is Br or Cl;

R₁ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—,

wherein n denotes an integer from 1 to 4;

R₂ is H or —CH₃; or

R is

Preferably, the copolymer macroinitiator is prepared from a mixture ofcabazole-containing norbornene-type monomer (II) and a macromonomer withthe formula (XV) in the presence of catalyst via ring-opening metathesispolymerization, wherein

wherein X is Br or Cl;

R₁ is —NH—, —O—, —(CH₂)n-NH—, or —(CH₂)n-O—,

wherein n denotes an integer from 1 to 4;

R₂ is H or —CH₃; or

R is

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 and FIG. 1A show 400MHz 1 HnmR spectrum of diblock copolymer,poly(CbzNB-b-NBMBr), containing carbazole groups and bromo-containingpolynorbornene segments (CDC₁₃ ).

FIG. 2 shows TGA curves for a diblock copolymer containing carbazole andbromo groups [poly(NBCbz-b-NBMBr)] and its hydrogenated diblockcopolymer [hydrogenated poly(NBCbz-b-NBMBr)] measured under air.Temperature was raised at a rate of 10° C.min⁻¹.

FIG. 3 and FIG. 3A show 400 MHz 1 HnmR spectrum obtained in CDCl₃ at 25°C. for a macromonomer containing norbornene end group (NBMPStBr).

FIG. 4 and FIG. 4A show 400 MHz 1 HnmR spectrum obtained in CDCl₃ at 25°C. for branched random poly(NBCbz-co-NBMPStBr).

FIG. 5 shows a schematic drawing for various architectures andpreparations according to the invention

DETAILED DESCRIPTION OF THE INVENTION

The norbornene monomers of the invention were prepared by Diels-Alderreaction at 180° C. in a high pressure reactor. Diels-Alder reaction wasthe reaction between diene and alkene to form forming a new cycloalkenemonomer. The reaction is not limited to the high-pressure reactor; allwell-known process for Diels-Alder reaction may be used in theinvention. After obtaining norbornene monomers with vinyl side chain orepoxy groups, polymers were further prepared by ring-opening metathesispolymerization (ROMP) of the monomers, such that various polymers may beprepared by reactions of different olefin groups and radicals.

The invention discloses a norbornene-type monomer as an initiator forradical polymerization, its polymer and fabrication method thereof. Forexample, a series of macromonomer, macroinitiator, grafted copolymer,random copolymers and diblock copolymers are disclosed.

First, halogen-containing norbornene-type initiators were prepared. Suchnorbornene-type initiators can be copolymerized with various functionalnorbornene-type monomers and the resulting copolymer-type initiatorsused to initiate radical polymerization of methyl methacrylate andstyrene for preparation of high performance polymeric materials.

According to the invention, the norbornene-type halogen-containingcompounds were prepared by Diels-Alder reaction in autoclaves at about180° C. The Diels-Alder reaction is a reaction of diolefin and olefinmonomers for producing cycloolefin derivatives. A series of ring-openedpolymers, macroinitiator and grafted copolymers can be produced byring-opening metathesis polymerization of the dislosed norbornene-typemonomer.

The norbornene-type monomers disclosed can also be combined with otherconventional monomers capable of undergoing ring-openingcopolymerization to form copolymers, if desirable. Examples of knownnorbornene-type monomers include norbornene and alkyl, alkylidene and/oraryl-substituted compounds thereof, such as 5-methyl-2-norbornene,5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene,5-ethylidene-2-norbornene, 5-phenyl-2-norbornene; dicyclopentadiene,2,3-dihydrodicyclopentadiene and substituted compounds thereof withalkyl such as methyl, ethyl, propyl, butyl, or the like;dimethanooctahydronaphthalene and alkyl, alkylidene and/oraryl-substituted compound thereof, such as6-methyl-1,4:5,8-dimethanol-1,4,4a,5,6,7,8,8a-octahydronaphthalene,6-ethyl-1,4:5,8-dimethanol-1,4,4a,5,6,7,8,8a-octahydronaphthalene,6-ethylidene-1,4:5,8-dimethanol-1,4,4a,5,6,7,8,8a-octahydronaphthalene,6-phenyl-1,4:5,8-dimethanol-1,4,4a,5,6,7,8,8a-octahydronaphthalene,etc.; trimers and tetramers of cyclopentadiene such as4,9:5,8-dimethano-3a,4,4a,5,8,8a,9,9a-octabydro-1H-benzonindene,4,11:5,10:6,9-trimethanol-3a,4,4a,5,5a,6,9,9a,10,10a,11,11a,22a-dodecahydro-1H-cyclopentaanthrace,etc.

In addition, the monomer may have a polar substituent or a substituenthaving a metal atom. Examples of such a substituent include halogenatoms such as chlorine, bromine and fluorine, ester-type moieties suchas methoxycarbonyl, ethoxycarbonyl and acetoxy groups, a cyano group,and a pyridyl group.

Conditions for ring-opening metathesis polymerization are described indetail as follows.

Metathesis Catalyst

Examples of tungsten and/or molybdenum-based metathesis catalystsinclude halides, oxyhalides or oxyorganic compounds thereof. Specificexamples thereof are tungsten hexachloride, tungsten (IV) oxycholride,tungsten tetrachloride, molybdenum pentachloride,acetylacetonatomolybdenum oxide, etc. In the invention, the catalystused for ring-opening metathesis polymerization (ROMP) is preferably{Cl₂Ru(CHPh)[P(C₆H₁₁)₃]₂}.

Solvent

The ring-opening polymerization of the norbornene-type monomer in thisinvention may be carried out in the absence of a solvent. However, it isgenerally carried out in an inert organic solvent.

For organic solvent, hydrocarbon solvents are preferred with cyclichydrocarbon solvents better able to dissolve the polymers formed by thering-opening polymerization particularly preferred. Specific examplesthereof include aromatic hydrocarbons such as benzene, ethylbenzene,toluene, xylene, etc.; aliphatic hydrocarbons such as n-pentane, hexane,heptane, etc.; alicyclic hydrocarbons such as cyclopentane, cyclohexane,methylcyclohexane, dimethylcyclohexane, decalin, etc.; hydrocarbonhalides such as methylene dichoride, dichloroethane, dichloroethylene,tetrachloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene,etc., or a combination thereof.

The quantity of solvent is based on 1 part by weight of the monomer,usually 1 to 20 parts by weight, preferably 2 to 10 parts by weight.

Polymerization Temperature

Temperatures for the ring-opening polymerization are not speciallylimited, preferably between −20° C. and 100° C., more preferably between0° C. and 100° C. and most preferably between 10° C. and 80° C.

Pressure for Polymerization System

The pressure for the polymerization ranges from 0 to 50 kg/cm²,preferably from ambient pressure to 10 kg/cm2 and more preferably notmore than 5 kg/cm².

Atmosphere for Polymerization System

The ring-opening polymerization is usually carried out in the presenceof an inert gas such as nitrogen, argon, or the like.

EXAMPLES

The invention is described further in detail as follows with referenceto examples, but is not limited thereto.

Bromo end group-containing norbornene-type monomer can be polymerized byring-opening metathesis polymerization(ROMP) to obtain polymericmaterials. Selectively, the bromo end group-containing norbornene-typemonomer can be used as an initiator to prepare various functionalpolymeric materials by polymerization of vinyl group-containingmonomers.

EXAMPLES

The invention is described further in detail as follows with referenceto examples, but is not limited thereto.

Example 1 Preparation of halogen-Containing Functional norbornene

The synthesis of (2-chloro methyl)bicyclo[2,2,1]hept-2-ene (norbornenemethylene chloride; NBMCl) (bp=54˜56° C./11 mmHg) and (2-bromomethyl)bicyclo[2,2,1]hept-2-ene (norbornene methylene bromide; NBMBr)(bp=75˜78° C./13 mmHg ) was accomplished via the Diels-Aldercondensation of freshly cracked dicyclopentadiene and correspondingallyl chloride and allyl bromide, respectively.

Preparation of halogen-containing functional norbornenes (NBMCl and/orNBMBr) was as follows:

wherein X is Br or Cl.

Example 2 Preparation of carbazole-Containing norbornene-Type monomer

12 g of potassium hydroxide (KOH) and 30 g of carbazole was added to 200ml of xylene. A potassium carbazole salt can be produced by removing thewater as a azeotrope by boiling with xylene from the solution. Thexylene was removed from the solution and replaced by DMF to act as asolvent. 25 g of 5-chlormethyl-2-norbornene was added to the solution,followed by refluxing for about 12 hours. After 12 hours, the resultingsolution was added to 200 ml of water and the mixture extracted with 100ml of ethyl acetate three times. After removing the ethyl acetate fromthe mixture by distillation, the residue obtained was purified by silicagel column chromatography using a mixture of solvent containing ethylacetate and n-hexane (ethyl acetate and n-hexane=1:6) as eluant. Thecarbazole-containing norbornene-type compound (the ratio of endoisomer:exo isomer is 3:2) with melting point of about 74-76° C. waspurified by recrystallization using hexane as solvent. Thecarbazole-containing norbornene-type monomer had the formula (i):

¹³C-NMR analysis (CDCl₃) δ (ppm): 140.4, 138.3, 136.5, 136.1, 132.4,125.5, 122.7, 120.1, 118.6, 108.8, 50.0, 48.1, 47.0, 45.0, 44.5, 44.0,42.6, 41.8, 39.0, 38.6, 30.8, 30.5. IR spectrum analysis (KBr PELLET.cm⁻¹): 1587(ν_(C═C), vinylic), 1647, 1478(ν_(C═C), aromatic stretching),1324(ν_(C—N),), 745, 718 (ν_(C—H), carbazole ring out of plane). UVspectrum analysis (THF): λ max=236.2 nm, ε=4.19×10⁴ Lmole⁻¹cm⁻¹.Elemental analysis (C₂₀H₁₉N): Calculated. C: 87.87%, H: 7.01%, N:5.12%.Found. C:87.58%, H:7.08%, N:5.31%.

Example 3 Preparation of carbazole-Containing Diblock MacroinitiatorHaving Various Segment Lengths Via ROMP Using {RuCl₂(CHPh)[P(C₆H₁₁)₃]₂}as a catalyst

The monomer, CbzNB, can be polymerized by living ROMP. Newmacroinitiator, poly(CbzNB-b-NBMBr), for radical polymerization wassynthesized by ROMP. A solution of catalyst was prepared by dissolving{RuCl₂(CHPh)[P(C₆H₁₁)₃]₂} (1.22×10⁻² mmol) in 1 mL of anhydrousmethylene chloride in an argon-filled drybox. The monomer CbzNB(9.8×10⁻³ mol) was dissolved in 4 mL of methylene chloride and degassedvia a freeze-pump-thaw cycle. After complete degassing, the catalystsolution was injected into the monomer solution by syringe. The pinksolution was vigorously stirred at 30° C. for 20 min. NBMBr (1.22×10⁻³mol) was injected to the still-living reaction mixture and the solutionwas stirred for another 12 hrs at 30° C. The solution changed from pinkto yellow after addition of NBMBr. The polymerization was terminated bythe addition of a small amount of ethyl vinyl ether (0.5 mL). Aftertermination, the solution was stirred for an additional 5 min andpoly(CbzNB-b-NBMBr) was precipitated in excess of methanol and driedovernight in a vacuum system at room temperature to give a flaky whitesolid.

In the ¹HnmR spectrum of poly(CbzNB-b-NBMBr) (FIG. 1 and FIG. 1A),signals due to the vinylic proton peaks of norbornene ring of NBMBr orCbzNB at about 5.90 and 6.00 ppm disappeared and the polymer showed newvinyl protons as broad signals between 5.10 and 5.80 ppm. Beforehydrogenation, the resonance signals between 5.10 and 5.80 ppm forpolynorbornene main chains and the aromatic resonances between 6.80 and8.10 ppm for CbzNB were observed.

Thermogravimetric analysis (TGA): The polymer was fairly stable up to orabove 300° C. as shown in FIG. 2.

Fluorescence emission: Poly(CbzNB-b-NBMBr) exhibited a strong carbazolefluorescence, with monomer emission occurring in the near-UV atapproximately 380 nm and extending into the blue-violet region (330 nmexcitation). A low-level emission observed at higher wavelengths (480nm) was probably due to excimer formation.

Preparation of poly(CbzNB-b-NBMBr) was as follows:

Example 4 Hydrogenation of the carbazole-Containing Macroinitiator

Poly(CbzNB-b-NBMX, X═Br or Cl) [Poly(CbzNB-b-NBMBr) orPoly(CbzNB-b-NBMCl)] (0.2 g ) was dissolved in 20 mL of xylene in anampoule. To the solution, 1.0 g of p-toluenesulfonylhydrazide as ahydrogenation agent and a trace of 2,6-di-tert-butyl-4-methylphenol wereadded. The ampoule containing the macroinitiator [Poly(CbzNB-b-NBMBr) orPoly(CbzNB-b-NBMCl)], solvent and hydrogenation agent was then degassedthrice via a freeze-pump-thaw cycle and sealed. The ampoule wasgradually heated to 120° C. A homogeneous solution resulted at 100° C.The solution was stirred at 120° C. for 3 hrs until the generation ofgas bubbles ceased. The solution was cooled to room temperature andprecipitated from methanol. The macroinitiator [HydrogenatedPoly(CbzNB-b-NBMBr) or Hydrogenated Poly(CbzNB-b-NBMCl)] was purified byreprecipitation from methanol. Hydrogenated macroinitiator [Hydrogenatedpoly(CbzNB-b-NBMBr) or Hydrogenated Poly(CbzNB-b-NBMCl)][Poly(HCbzNB-b-HNBMBr) or Poly(HCbzNB-b-HNBMCl)] was dried byfreeze-drying.

In the ¹HnmR spectrum of hydrogenated poly(CbzNB-b-HNBMBr), theresonances between 5.10 and 5.80 ppm due to protons of the double bondof polynorbornene main chain ceased and the aromatic resonances between6.80 and 8.10 ppm for CbzNB appeared. The resonances between 0.50 and4.50 ppm for aliphatic polynorbornene main chain were observed.

Thermogravimetric analysis (TGA): The polymer was fairly stable up to orabove 420° C. as shown in FIG. 2(b).

Fluorescence emission: Hydrogenatedpoly(CbzNB-b-NBMBr)[poly(HCbzNB-b-HNBMBr)] exhibited a strong carbazolefluorescence, with monomer emission occurring in the near-UV atapproximately 380 nm and extending into the blue-violet region (330 nmexcitation). A low-level emission observed at higher wavelengths (480nm) was probably due to excimer formation.

Hydrogenation of these carbazole-containing macroinitiators was asfollows:

Example 5 Preparation of macromonomers With norbornene End Group

Functional norbornenes containing halo end group in the invention areemployed as initiators in order to prepare poly(methyl methacrylate) andpoly(styrene) via radical polymerization of methyl methacrylate andstyrene, respectively.

The structures of norbornene-containing macromonomers are as follows:

wherein X is Br or Cl; and

R is poly(methyl methacrylate) or poly(styrene).

Example 6 Preparation of poly(MMA) With norbornene methylene End Group,NBMPMMA

To an ampoule, Cu(I)Br (1 mmol), 2,2′-bipyridine (1 mmol), norbornenemethylene bromide(NBMBr) (1 mmol), methyl methacrylate(MMA) (100 mmol)and toluene (10 mL) were added. The heterogeneous mixture was placedunder vacuum and degassed via a freeze-pump-thaw cycle thrice. Afterdegassing, the reaction mixture in ampoule was stirred at 130° C. for 12hrs. The polymer was precipitated from methanol and reprecipitated intomethanol three times. A new macromonomer of α-norbornene methylenepoly(methyl methacrylate)(NBMPMMA) was obtained. Mn=1.80×10⁵ and PDI=1.3by GPC (n=1800).

Preparation of norbornene-containing macromonomer with bromo end groupwas as follows:

Cu(I)Br (1 mmol), 2,2′-bipyridine (1 mmol), norbornene methylenechloride (NBMCl) (1 mmol), methyl methacrylate (100 mmol) and toluene(10 mL) were used for preparation of choro-containing macromonomer asfollows:

Example 7 Preparation of poly(styrene) With norbornene methylene EndGroup, NBMPSt

To an ampoule, Cu(I)Br (0.38 g), 2,2′-bipyridine (1.25 g), norbornenemethylene bromide (NBMBr) (0.5 g), styrene (8 g) and toluene (10 mL)were added. The heterogeneous mixture was placed under vacuum anddegassed via a freeze-pump-thaw cycle thrice. After degassing, thereaction mixture in ampoule was stirred at 130° C. for 12 hrs. Thepolymer was precipitated from methanol and reprecipitated from THF intomethanol three times. A new macromonomer of α-norbornene methylenepolystyrene (NBMPSt) was obtained. Mn=1.60×10⁵ and PDI=1.26 by GPC.

Thermal property: NBMPSt macromonomer ( Mn=1.60×10⁵) had a Tg of 107° C.(By DSC) for polystyrene segment.

400 MHz ¹HnmR spectrum obtained in CDCl₃ at 25° C. for NBMPStmacromonomer was shown in FIG. 3.

Preparation of NBMPSt macromonomer was as follows:

Example 8 Preparation of halogen-Containing polynorbornene

NBMBr (2.5 mmol) was dissolved in 4 mL of methylene chloride(CH₂Cl₂).After degassing by freeze-pump-thaw cycle, the solution of{RuCl₂(CHPh)[P(C₁₈H₁₅)]₂} (2.5×10⁻³ mmol) in 1 mL of methylene chloridewas injected to the monomer solution. The solution was stirred for 2 hrsat 30° C. The reaction was terminated by the addition of a trace amountof ethyl vinyl ether (0.1 mL). The solution was continuously stirred foranother 10 min and the polymer precipitated in excess of methanol.Poly(NBMBr) was obtained. NBMBr can be polymerized by ring-openingmetathesis polymerization (ROMP) even containing functional bromo-endgroup of monomer. The high functional group tolerance of{RuCl₂(CHPh)[P(C₁₈H₁₅)]₂} has prompted an investigation of the use it asring-opening metathesis polymerization (ROMP) catalyst in the formationof macroinitiators for radical polymerization.

The structure was as follows:

wherein X is Br or Cl.

Example 9 Preparation of a Grafted copolymer With PMMA Derived from thebromo-Containing Macroinitiator Via Radical polymerization

To an ampoule, Cu(I)Br (1 mmol), 2,2′-bipyridine (1 mmol), poly(NBMBr),(1 mmol) and methyl methacrylate(MMA) (100 mmol) were added in 10 mLtoluene. The heterogeneous mixture was placed under vacuum and degassedvia a freeze-pump-thaw cycle thrice. After degassing, the reactionmixture in ampoule was stirred at 100° C. for 12 hrs. The polymer wasprecipitated from methanol; dissolved in THF, and reprecipitated frommethanol three times.

Graft copolymerization of bromo-containing macroinitiator [poly(NBMBr)]with methyl methacrylate (MMA) in toluene solution was as follows:

Bulk graft copolymerization of bromo-containing macroinitiatorpoly(NBMBr) was as follows:

The reaction of poly(NBMCl) with Cu(I)Br and 2,2′-bipyridine in toluenewas as follows:

Bulk graft copolymerization of chloro-containing macroinitiatorpoly(NBMCl) was as follows:

Example 10 Hydrogenation of Functional polynorbornenes Containing haloSide Group, poly{(2-bromo methyl)bicyclo[2,2,11hept-2-ene}[poly(NBMBr)]or poly{(2-chloro methyl)bicyclo[2,2,1]hept-2-ene}[poly(NBMCl)]

A functional polynorbornene containing halo side group, poly{(2-bromomethyl)bicyclo[2,2,1]hept-2-ene}[poly(NBMBr)] or poly{(2-chloromethyl)bicyclo[2,2,1]hept-2-ene}[poly(NBMCl)], (0.5 g) was dissolved in50 mL of xylene in an ampoule. To the solution, 2.75 g (7.5 equiv.relative to the repeating unit) of p-toluenesulfonylhydrazide as ahydrogenation agent and a trace of 2,6-di-tert-butyl-4-methylphenol wereadded. The ampoule containing the polymer, solvent and hydrogenationagent was then degassed thrice via a freeze-pump-thaw cycle and sealed.Then, it was gradually heated to 120° C. A homogeneous solution resultedat 100° C. The solution was stirred at 120° C. for 3 hr until thegeneration of gas bubbles ceased. The solution was cooled to roomtemperature and precipitated in methanol. The polymer was purified byreprecipitation in methanol. The hydrogenated polymer, hydrogenatedpoly(NBMBr) or hydrogenated poly(NBMCl), was dried under vacuumovernight at room temperature.

The synthetic scheme is shown as the following:

wherein X is Br or Cl.

Example 11 Preparation of a Grafted copolymer With PMMA Using thehydrogenated bromo-containing Macroinitiator[hydrogenated poly(NBMBr) orhydrogenated poly(NBMCI)] Via ATRP

To an ampoule, Cu(I)Br (1 mmol), 2,2′-bipyridine (1 mmol), poly(NBMBr),(1 mmol) and methyl methacrylate(MMA) (100 mmol) were added in 10 mLtoluene. The heterogeneous mixture was placed under vacuum and degassedvia a freeze-pump-thaw cycle thrice. After degassing, the reactionmixture in ampoule was stirred at 100° C. for 12 hrs. The polymer wasprecipitated from toluene into methanol; dissolved in THF andreprecipitated from methanol three times.

The reaction in toluene was as follows:

The bulk polymerization was as follows:

The reaction of norbornene chloride with Cu(I)Br and 2,2′-bipyridine intoluene was as follows:

The bulk reaction of norbornene chloride with Cu(I)Br and2,2′-bipyridine was as follows:

Example 12 Preparation of a Functional copolynorbornene Containingcarbazole Groups and polystyrnene Segments

To an ampoule, Cu(I)Br (1 mmol), 2,2′-bipyridine (1 mmol), norbornenemethylene bromide(NBMBr) (1 mmol) and styrene(St) (100 mmol) were addedin 10 mL toluene. The heterogeneous mixture was placed under vacuum anddegassed via a freeze-pump-thaw cycle thrice. After degassing, thereaction mixture in ampoule was stirred at 100° C. for 12 hrs. Themacromonomer containing polystyrene segments (NBMPStBr) was precipitatedfrom methanol. Polymer was dissolved in THF and reprecipitated frommethanol three times. Number average molecular weight of (NBMPStBr) is160000 and PDI is 1.28 (by GPC).

Furthermore, copolymerization of a macromonomer containing polystyrenesegments (NBMPStBr) and a carbazole-containing norbornene derivative wascarried out by ring-opening metathesis polymerization. A functionalcopolynorbornene containing carbazole groups and polystyrnene segmentswas obtained.

The ¹HnmR (400 MHz) spectrum of branched random poly(NBCbz-co-NBMPStBr)obtained in CDCl₃ at 25° C. which is shown in FIG. 4 and FIG. 4A.

Number average molecular weight of poly(NBCbz-co-NBMPStBr) is 399000 andPDI is 1.30 yield=95%.

Thermal properties were determined by DSC:

Tg=105° C.[Poly(styrene) segment] and Tg=165° C.[Poly(NBCbz) segment].

The structure of poly(NBCbz-co-NBMPStBr) was as follows:

Example 13 Preparation of norbornene methylene amine (NBMA)

The norbornene derivative of norbornene methylene amine (NBMA) is mainlyproduced by the reaction of cyclopentadiene (66 g) and allyl amine (50g). The required reaction condition of the Diels-Alder reaction in theinvention is usually controlled at 180° C. for 8 hrs in the presence ofhydroquinone (1 g) as a inhibitor. The boiling point of allyl amine is55-58° C., so the reaction needs to be carried out in autocalve. Theresulting solution is distilled under vacuum to obtain norbornenemethylene amine (NBMA) (bp=59˜61° C./11 mmHg).

Synthetis was as follows:

Example 14 Preparation of a Functional norbornene Containing2-bromo-2-methyl propionyl End Group [2-bromo-2-methyl propionylmethyl]bicyclo[2,2,1]hept-2-ene; NBTMBr]

The monomer, (2-bromo-2-methyl propionyl methyl)bicyclo[2,2,1]hept-2-ene, was prepared via the reaction of5-norbornen-2-methylene amine(NBMA) and 2-bromo-2-methylpropionylbromide. A solution of 5-norbornen-2-methylene amine (1.11 g, 1 mmol) inmethylene chloride (30 mL) and triethylamine (TEA) (1.01 g, 1 mol) werecharged into a flask (150 mL) maintained at 0° C. in an ice bath.2-Bromo-2-methylpropionyl bromide (2.30 g, 1 mol) was dissolved inmethylene chloride (20 mL), then added to the solution by a drop funnelover a period of 30 min and stirred for another hour. After completionof the reaction, the organic layer was washed with distilled water (fourtimes) and dried over sodium sulfate. After removing the solvent, alight yellow solid, 2-bromo-2-methyl propionyl-containing functionalnorbornene derivative[(2-bromo-2-methyl propionyl methyl)bicyclo[2,2,1]hept-2-ene; NBTMBr], was obtained. The functionalnorbornene monomer [(2-bromo-2-methyl propionyl methyl)bicyclo[2,2,1]hept-2-ene; NBTMBr] was purified by crystallization fromn-hexane; m.p.=84.9° C. (by DSC) and exo/endo was measured to be 15:85both by ¹HnmR and ¹³CnmR spectroscopies. Elemental ANAL. Calculated forC₁₅H₂₁O₄N: C, 52.94%; H, 6.62%; N, 5.15%; found: C, 52.80%; H, 6.52%; N,4.98%. The ¹HnmR and ¹³CnmR spectra of the functional norbornene monomer[(2-bromo-2-methyl propionyl methyl)bicyclo[2,2,1]hept-2-ene; NBTMBr]agree satisfactorily with the proposed structure.

¹HnmR (CDCl₃): δ(ppm)=0.5 (H_(n3n)), 1.2 (H_(x3x)), 1.3 (H_(n7a)), 1.37(H_(n7s)), 1.5 (H_(x7as)), 1.54 (H_(x2n)), 1.7 (H_(n3x)), 1.8 (H₁₀), 2.2(H_(n2x)), 2.54 (H_(x4)), 2.75 (H_(n4)), 2.78(H_(x1)), 2.85(H_(x1)), 2.9(H_(x8)), 2.97 (H_(x8)) , 5.9 (H_(n6)), 6.0 (H_(x5),H_(x6)), 6.1(H_(n5)), 6.73 (H_(g)). ¹³CnmR (CDCl₃): δ(ppm)=30 (C_(n3n)), 30.7(C_(n3n)), 32.6 (C₁₀), 38.7 (C_(x2)), 39.0 (C_(n2x)), 42.5(C₃), 44.3(C_(x1)), 44.4 (C_(x4)), 45.2 (C_(n4)), 45.6 (C_(n1)), 49.7 (C_(x7)),63.5 (C_(n8)), 132.1 (C_(n7)), 136.3 (C_(x6)), 137 (C_(n5)), 171.5 (C₉).

Melting point: 84.9° C.

Solubility: 2-Bromo-2-methyl propionyl-containing functional norbornenederivative[(2-bromo-2-methyl propionyl methyl)bicyclo[2,2,1]hept-2-ene;NBTMBr] is soluble in acetone, pyridine, ethanol, methanol, methylenechloride, tetrahydrofuran, N,N-dimethylformamide (DMF) anddimethylsulfoxide (DMSO) at room temperature; completely inN,N-dimethylacetamide (DMAC) at 60° C.; and partially in toluene,benzene, hexane and N-methyl-2-pyrrolidinone (NMP) at 60° C.

The preparation of 2-bromo-2-methyl propionyl-containing functionalnorbornene derivative [(2-bromo-2-methyl propionylmethyl)bicyclo[2,2,1]hept-2-ene; NBTMBr] was as follows:

Similarly, various functional norbornene derivatives can be obtained asfollows:

Example 15 Preparation of polynorbornene Containing bromo-Side Group,(2-bromo-2-methyl propionylmethyl)bicyclo[2,2,1]hept-2-ene[poly(NBMBrMP)]

For example, preparation of functional polynorbornene containing2-bromo-2-methyl propionyl-side group, (methyl)bicyclo[2,2,1]hept-2-ene[poly(NBMBrMP)] is carried out with [M]/[I]=520. A solution of catalystwas prepared by dissolving RuCl2(CHPh)[P(C6H11)3]2 (0.001 g, 1.22×10−6mol) in 1 mL of anhydrous methylene chloride in an argon-filled dry box.The monomer (0.22 g, 1.22×10−3 mol) was dissolved in 5 mL of methylenechloride and degassed via a freeze-pump-thaw cycle. After completedegassing of the reaction mixture, the catalyst solution was injectedinto the monomer solution by syringe. The pink solution was vigorouslystirred at room temperature for 24 hr and the color changed from pink toyellow. The reaction was terminated by the addition of a small amount ofethyl vinyl ether (0.5 mL). After termination, the solution was stirredfor an additional 5 min and the polymer, poly(NBMBrMP), was precipitatedin excess of methanol and dried overnight in a vacuum system at roomtemperature to give a flaky white solid.

¹HnmR (CDCl₃): δ(ppm)=5.5˜5.2 (H₅, H₆), 1.9 (H₁₀), 7.2 (H₉), 3.8˜0.8(H₁, H₂, H₃, H₄, H₇, H₈). ¹³CnmR (CDCl₃): δ 24.6˜52.5 (C₁, C₂, C₃, C₄,C₈), 67.0 (C₁₁), 129.0˜134.1 (C₅, C₆), 170.8 (C₁₂). The ¹HnmR and ¹³CnmRspectra agree satisfactorily with the proposed structure.

Polymerization of the functional norbornene containing a halo end groupwas carried out with various [M]/[I] ratios by ring-opening metathesispolymerization. The resulting functional polynorbornene with variousmolecular weights and PDI values derived from the functional norbornenewas obtained. [M]/[I]=260, Mn=45000, Mw/ Mn=1.22; [M]/[I]=425,Mn=138000, Mw/ Mn=1.33; [M]/[I]=520, Mn=139000, Mw/ Mn=1.35;[M]/[I]=780, Mn=200000, Mw/ Mn=1.42; [M]/[I]=1100, Mn=314000, Mw/Mn=1.56.

Solubility : The poly(NBMBrMP) ([M]/[I]=520 ) containing bromo sidechains is soluble in pyridine, methylene chloride, tetrahydrofuran(THF),N,N-dimethylformamide(DMF) and N-methyl-2-pyrrolidinone (NMP) at roomtemperature; completely in benzene, N,N-dimethylacetamide (DMAc) anddimethylsulfoxide (DMSO) at 60° C.; and partially in toluene at 60° C.

Synthesis was as follows:

Example 16 Hydrogenation of polynorbornene Containing bromo-Side Group,poly{(2-bromo-2-methylpropionylmethyl)bicyclo[2,2,1]Hept-2-ene}[Poly(NBMBrMP)]

Poly(NBMBrMP) (0.5 g) was dissolved in 50 mL of xylene in an ampoule. Tothe solution 2.75 g (7.5 equiv. relative to the repeating unit) ofp-toluenesulfonylhydrazide as a hydrogenation agent and a trace of2,6-di-tert-butyl-4-methylphenol were added. The ampoule containing thepolymer, solvent and hydrogenation agent was then degassed thrice via afreeze-pump-thaw cycle and sealed. Then, it was gradually heated to 120°C. A homogeneous solution resulted at 100° C. The solution was stirredat 120° C. for 3 hr until the generation of gas bubbles ceased. Thesolution was cooled to room temperature and polymer was precipitated inmethanol. The polymer was purified by reprecipitation in methanol. Thehydrogenated polymer, hydrogenated poly(NBMBrMP), was dried under vacuumovernight at room temperature.

¹HnmR (CDCl₃): δ0.8˜3.8 (H₁, H₂, H₃, H₄, H₅, H₆, H₇, H₈), 1.9 (H₁₀), 6.7(H₉). ¹³CnmR (CDCl₃): δ 18.7˜50.0 (C₁, C₂, C₃, C₄, C₈), 67.7 (C₁₁),170.8 (C₁₂).

Solubility: The hydrogenated poly(NBMBrMP) was soluble in pyridine andmethylene chloride at room temperature; completely inN,N-dimethylacetamide (DMAc) and N,N-dimethylformamide (DMF) at 60° C.;and partially in tetrahydrofuran(THF), ethyl acetate (EA),N-methyl-2-pyrrolidinone (NMP) and dimethylsulfoxide (DMSO) at 60° C.

Synthesis was as follows:

Example 17 Synthesis of Grafted copolymer of hydrogenated poly(NBMBRMP)With polymethyl methacrylate Via ATRP

To an ampoule, Cu(I)Br (0.143 g), 2,2′-bipyridine (0.156 g),hydrogenated poly(NBMBrMP)[poly(HNBMBrMP), Mn=1.3×10⁴, PDI=1.9] (0.5 g)and methyl methacrylate (1 g) were added in 50 mL toluene. Theheterogeneous mixture was placed under vacuum and degassed via afreeze-pump-thaw cycle thrice. After degassing, the reaction mixture inthe ampoule was stirred at 100° C. for 12 hr. The polymer,poly(HNBMBrMP-g-PMMA) [ Mn=2.0×10⁴, PDI=1.9], was precipitated frommethanol. The polymer was purified by dissolving in THF andreprecipitating from methanol three times. ¹HnmR (CDCl₃): δ(ppm)=0.8˜3.8 (H₁, H₂, H₃, H₄, H₇, H₈), 1.9 (H₁₀), 6.7 (H₉). ¹³CnmR(CDCl₃): δ 29.9˜63.9 (C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C_(e), C_(f),C_(g)), 172.1˜172.3 (C_(i), C₁₂).

Synthesis was as follows:

Example 18 Preparation of bromo-Containing α-norbornyl polymethylmethacrylate macromonomer (NBPMMA) Via Atom Transfer Radicalpolymerization

Simple alkyl halides were used for atom transfer radical polymerizationas initiators and copper(I) complexes as catalysts. Both of these areinexpensive and readily available.

To an ampoule, Cu(I)Br (0.71 g), 2,2′-bipyridine (0.65 g),2-bromo-2-methyl propionyl methyl}bicyclo[2,2,1]hept-2-ene (1.3 g) andmethacrylate (5 g) were added. The heterogeneous mixture was placedunder vacuum and degassed via a freeze-pump-thaw cycle thrice. Afterdegassing, the reaction mixture in the ampoule was stirred at 100° C.for 12 hrs. The polymer was purified by dissolving in THF andreprecipitating from methanol three times. Mn=6.4×10³ and PDI=1.5 asmeasured by GPC. Yield=72%. The ¹HnmR spectrum of the α-norbornylpolymethyl methacrylate macromonomer (NBPMMA) was recorded. The signalsassociated with the vinylic protons of norbornene were observed at5.17˜5.28 ppm. The signals due to saturated chain were in the region(1.0˜3.5 ppm) and polymethyl methacrylate segment [—CH ₂C(CH₃)COOCH₃:2.10 ppm; —CH₂C(CH ₃)COOCH₃: 0.87, 1.04, 1.90 ppm; —CH₂C(CH₃)COOCH ₃:3.60 ppm] of the spectrum provided further confirmation of themacromonomer (NBPMMA) structure. ³CnmR (CDCl₃): δ 17.0˜68.0 (C₁, C₂, C₃,C₄, C₇, C₈, C_(e), C_(f), C_(g)), 127.0˜130.0 (C₅, C₆), 175.0˜180.0(C_(h), C₁₂). The macromonomer (NBPMMA) had a glass transitiontemperature (Tg) of 110° C. for polymethyl methacrylate segment.

The macromonomer with various average number molecular weight ( Mn) andPDI values were prepared with various reaction times. The macromonomerwith Mn=12900 and Mw/ Mn=1.37 was obtained after 12 hrs. Themacromonomer with Mn=14700, Mw/ Mn=1.44 was obtained after 24 hrs. Themacromonomer with Mn=16600, Mw/ Mn=1.55 was obtained after 48 hrs.

Solubility: Macromonomer (NBPMMA) is soluble in methylene chloride,tetrahydrofuran(THF), N,N-dimethylacetamide (DMAc), pyridine anddichorobenzene at room temperature and in acetone, pyridine, benzene,N,N-dimethylformamide (DMF), ethyl acetate (EA),N-methyl-2-pyrrolidinone (NMP) and dimethylsulfoxide (DMSO) at 60° C.

Synthesis was as follows:

Example 19 Preparation of poly[α-norbornyl polymethyl methacrylatemacromonomer-co-5-(N-carbazolyl methyl)bicyclo[2.2.1]hept-2-en],poly(NBPMMA-co-NBCbz), via Ring-Opening metathesis polymerization

The α-norbornyl polymethyl methacrylate macromonomer (NBPMMA) withmolecular weight ( Mn) exceeding 1.29×10⁴ could not be homopolymerizedvia ring-opening metathesis polymerization (ROMP) by Ru catalyst[(Cy₃P)₂Cl₂Ru═CHPh, Cy=cyclohexyl]. Copolymerization was carried outwith norbornene derivative such as 5-(N-carbazolylmethyl)bicyclo[2.2.1]hept-2-ene (NBCbz). The resulting copolymerexhibited electro-optical properties and good thermal stability.

A catalyst solution was prepared by dissolving 1 mg of[(Cy₃P)₂Cl₂Ru═CHPh, Cy=cyclohexyl] in 1 mL of anhydrous methylenechloride under an argon-filled drybox. The α-norbornyl polymethylmethacrylate macromonomer (NBPMMA) (0.1 g) with Mn=1.29×10⁴ and NBCbz(0.1 g) were dissolved in 5 mL of methylene chloride and the reactionmixture was degassed via a freeze-pump-thaw cycle thrice. After it wasdegassed completely, the catalyst solution was injected into the mixtureby a syringe. The reaction mixture was stirred at 25° C. for 2 hrs. Therandom copolymer was precipitated from methanol and purified bydissolving in THF and reprecipitating from methanol three times.Mn=4.76×10⁴ and PDI=1.78 (GPC). The structure of poly(NBPMMA-co-NBCbz)was confirmed by ¹HnmR spectroscopy.

The synthetic scheme is shown as following:

Furthermore, various architectures and preparations according toinvention can be described with reference to a schematic drawing asshown in FIG. 5.

The invention provides a series of norbornene-type monomers which caninitiate free-radical polymerization and a method for preparationthereof. A series of polymeric derivatives can be obtained byring-opening metathesis polymerization, grafting polymerization andradical polymerization. The molecular weights of resulting polymericderivatives are controllable. The polymers disclosed in the inventionare transparent, excellent in heat resistance and opticalcharacteristics. The resulting polymeric derivatives not only show thespecific characteristic due to norbornene and polynorbornene but alsoprovide an enhanced property.

While the invention has been described in terms of preferred embodiment,it is to be understood that the invention is not limited thereto. On thecontrary, it is intended to cover various modifications and similararrangements included within the spirit and scope of the appended claimswhich are to be accorded with the broadest interpretation so as toencompass all such modifications and similar structures. Therefore, theabove description and illustration should not be taken as limiting thescope of the invention which is defined by the appended claims.

1. A polynorbornene-containing grafted copolymer comprising the formula(IVA), prepared by graft copolymerization using a diblock macroinitiatorwith the formula (IV):

wherein X is Br or Cl; and Ar is


2. The polynorbornene-containing grafted copolymer as claimed in claim1, wherein the diblock macroinitiator with the formula (IV) is preparedby hydrogenating a diblock macroinitiator with the formula (I),

wherein X is Br or Cl.
 3. A method for preparing a graftedpolynorbornene with the formula (IVA), comprising: preparation of amacroinitiator with the formula (I) by reaction of cabazole-containingnorbornene-type monomer (II) and a catalyst via ring-opening metathesispolymerization and an additional norbornene dervative(III) added to themixture after 15˜120 mins of ring-opening metathesis polymerization;hydrogenation of the diblock macroinitiator with the formula (I) toprepare a thermally-stable saturated cyclic aliphatic diblockmacroinitiator with the formula (IV); preparation of a mixture ofCu(I)Br,2,2′-bipyridine, the thermally-stable saturated cyclic aliphaticdiblock macroinitiator (IV) and a monomer of

preparation of the grafted polynorbornene copolymer with the formula(IVA) by a graft copolymerization of the mixture at various temperaturesfrom 50 to 150° C., wherein

wherein X is Br or Cl; and R is


4. A thermally-stable saturated cyclic aliphatic diblock macroinitiatorcomprising the formula (IV), prepared by hydrogenating a diblockmacroinitiator with the formula (I),

wherein X is Br or Cl.